Surface modification and oxygen reduction on glassy carbon in chloride media

The reduction of oxygen on rotating disk glassy carbon electrodes was studied in 0.1M HCl. Reproducible single waves with constant limiting currents over a potential range of 0.5V were obtained after the samples were electrochemically treated: anodic polarization at 2.0V vs. SCE and subsequent cathodic reduction. The number of electrons transferred in the oxygen reduction reaction was calculated to be 2.3. The surface of the glassy carbon was examined by XPS at different stages of the electrochemical treatment. After the anodic treatment, the ratio of oxidized carbon vs. graphitic carbon was higher than 1. The predominant oxygen species were carbonyl groups. Following reduction, the surface had an oxidized vs. graphitic carbon ratio below 0.5 with the oxygen distributed between phenolic and carboxylic groups. The role of the chloride ion in the formation of the carbonyl groups is discussed.